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Exposing the Delocalized Cu−S π Bonds on the Au 24 Cu 6 (SPh t Bu) 22 Nanocluster and Its Application in Ring‐Opening Reactions
Author(s) -
Chai Jinsong,
Yang Sha,
Lv Ying,
Chong Hanbao,
Yu Haizhu,
Zhu Manzhou
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201907609
Subject(s) - bimetallic strip , epoxide , catalysis , delocalized electron , ring (chemistry) , chemistry , copper , crystallography , benzene , organic chemistry
Abstract Bimetallic nanomaterials are of major importance in catalysis. A Au‐Cu bimetallic nanocluster was synthesized that is effective in catalyzing the epoxide ring‐opening reaction. The catalyst was analyzed by SCXRD and ESI‐MS and found to be Au 24 Cu 6 (SPh t Bu) 22 (Au 24 Cu 6 for short). Six copper atoms exclusively occupy the surface positions in two groups with three atoms for each, and each group was bonded with three thiolate ligands to give a planar motif reminiscent of a benzene ring. In the epoxide‐ring opening reaction, Au 24 Cu 6 exhibited superior catalytic activity compared to other homometallic and Au‐Cu alloy NCs, such as Au 25 and Au 38− x Cu x . Control experiments and DFT calculations revealed that the π conjugation among the Cu−S bonds played a pivotal role. This study demonstrates a unique π conjugation established among the Cu−S bonds as a critical structural motif in the nanocluster, which facilitates the catalysis of a ring‐opening reaction.